Semiconductor Device and Methods of Manufacture

ABSTRACT

A semiconductor device and method of manufacture are provided. In an embodiment a metal layer is formed over a substrate using a fluorine-free deposition process, a nucleation layer is formed over the metal layer using a fluorine included deposition process, and a fill material is formed to fill an opening and form a gate stack.

PRIORITY

This application is a continuation of U.S. patent application Ser. No.16/206,324, filed on Nov. 30, 2018, entitled “Semiconductor Device andMethods of Manufacture,” which application is a division of U.S. patentapplication Ser. No. 15/783,153, filed on Oct. 13, 2017, entitled“Semiconductor Device and Methods of Manufacture,” now U.S. Pat. No.10,269,569, issued on Apr. 23, 2019, which application claims priorityto and the benefit of U.S. Provisional Application No. 62/427,526, filedon Nov. 29, 2016, entitled “Fluorine-Free Barrier for Metal GateDevice,” which applications are hereby incorporated herein by reference.

BACKGROUND

Semiconductor devices are used in a variety of electronic applications,such as, for example, personal computers, cell phones, digital cameras,and other electronic equipment. Semiconductor devices are typicallyfabricated by sequentially depositing insulating or dielectric layers,conductive layers, and semiconductor layers of material over asemiconductor substrate, and patterning the various material layersusing lithography to form circuit components and elements thereon.

The semiconductor industry continues to improve the integration densityof various electronic components (e.g., transistors, diodes, resistors,capacitors, etc.) by continual reductions in minimum feature size, whichallow more components to be integrated into a given area. However, asthe minimum features sizes are reduced, additional problems arise thatshould be addressed.

BRIEF DESCRIPTION OF THE DRAWINGS

Aspects of the present disclosure are best understood from the followingdetailed description when read with the accompanying figures. It isnoted that, in accordance with the standard practice in the industry,various features are not drawn to scale. In fact, the dimensions of thevarious features may be arbitrarily increased or reduced for clarity ofdiscussion.

FIG. 1 illustrates steps in a process of forming a finFET device inaccordance with some embodiments.

FIG. 2 illustrates formation of source/drain regions in accordance withsome embodiments.

FIG. 3 illustrates a formation of a first opening and deposition oflayers of a gate stack in accordance with some embodiments.

FIGS. 4A-4C illustrate a formation of a metal layer in accordance withsome embodiments.

FIG. 5 illustrates a formation of a nucleation layer in accordance withsome embodiments.

FIG. 6 illustrates a deposition of a fill material in accordance withsome embodiments.

FIG. 7 illustrates a formation of a capping layer in accordance withsome embodiments.

FIG. 8 illustrates formation of a first contact in accordance with someembodiments.

FIG. 9 illustrates a formation of second contacts in accordance withsome embodiments.

FIGS. 10A-10B illustrate charts of chlorine and fluorine in accordancewith some embodiments.

DETAILED DESCRIPTION

The following disclosure provides many different embodiments, orexamples, for implementing different features of the invention. Specificexamples of components and arrangements are described below to simplifythe present disclosure. These are, of course, merely examples and arenot intended to be limiting. For example, the formation of a firstfeature over or on a second feature in the description that follows mayinclude embodiments in which the first and second features are formed indirect contact, and may also include embodiments in which additionalfeatures may be formed between the first and second features, such thatthe first and second features may not be in direct contact. In addition,the present disclosure may repeat reference numerals and/or letters inthe various examples. This repetition is for the purpose of simplicityand clarity and does not in itself dictate a relationship between thevarious embodiments and/or configurations discussed.

Further, spatially relative terms, such as “beneath,” “below,” “lower,”“above,” “upper” and the like, may be used herein for ease ofdescription to describe one element or feature's relationship to anotherelement(s) or feature(s) as illustrated in the figures. The spatiallyrelative terms are intended to encompass different orientations of thedevice in use or operation in addition to the orientation depicted inthe figures. The apparatus may be otherwise oriented (rotated 90 degreesor at other orientations) and the spatially relative descriptors usedherein may likewise be interpreted accordingly.

Embodiments will be described below with respect to specificembodiments, including a replacement metal gate for use with 10 nmtechnology nodes or smaller. Embodiments, however, are not intended tobe limited, and may be utilized in a wide variety of embodiments beyondthe 10 nm technology node.

With reference now to FIG. 1, there is illustrated a perspective view ofa semiconductor device 100 such as a finFET device. In an embodiment thesemiconductor device 100 comprises a substrate 101 and first trenches103. The substrate 101 may be a silicon substrate, although othersubstrates, such as semiconductor-on-insulator (SOI), strained SOI, andsilicon germanium on insulator, could be used. The substrate 101 may bea p-type semiconductor, although in other embodiments, it could be ann-type semiconductor.

The first trenches 103 may be formed as an initial step in the eventualformation of first isolation regions 105. The first trenches 103 may beformed using a masking layer (not separately illustrated in FIG. 1)along with a suitable etching process. For example, the masking layermay be a hardmask comprising silicon nitride formed through a processsuch as chemical vapor deposition (CVD), although other materials, suchas oxides, oxynitrides, silicon carbide, combinations of these, or thelike, and other processes, such as plasma enhanced chemical vapordeposition (PECVD), low pressure chemical vapor deposition (LPCVD), oreven silicon oxide formation followed by nitridation, may be utilized.Once formed, the masking layer may be patterned through a suitablephotolithographic process to expose those portions of the substrate 101that will be removed to form the first trenches 103.

As one of skill in the art will recognize, however, the processes andmaterials described above to form the masking layer are not the onlymethod that may be used to protect portions of the substrate 101 whileexposing other portions of the substrate 101 for the formation of thefirst trenches 103. Any suitable process, such as a patterned anddeveloped photoresist, may be utilized to expose portions of thesubstrate 101 to be removed to form the first trenches 103. All suchmethods are fully intended to be included in the scope of the presentembodiments.

Once a masking layer has been formed and patterned, the first trenches103 are formed in the substrate 101. The exposed substrate 101 may beremoved through a suitable process such as reactive ion etching (RIE) inorder to form the first trenches 103 in the substrate 101, although anysuitable process may be used. In an embodiment, the first trenches 103may be formed to have a first depth of less than about 5,000 Å from thesurface of the substrate 101, such as about 2,500 Å.

However, as one of ordinary skill in the art will recognize, the processdescribed above to form the first trenches 103 is merely one potentialprocess, and is not meant to be the only embodiment. Rather, anysuitable process through which the first trenches 103 may be formed maybe utilized and any suitable process, including any number of maskingand removal steps may be used.

In addition to forming the first trenches 103, the masking and etchingprocess additionally forms fins 107 from those portions of the substrate101 that remain unremoved. For convenience the fins 107 have beenillustrated in the figures as being separated from the substrate 101 bya dashed line, although a physical indication of the separation may ormay not be present. These fins 107 may be used, as discussed below, toform the channel region of multiple-gate FinFET transistors. While FIG.1 only illustrates three fins 107 formed from the substrate 101, anynumber of fins 107 may be utilized.

The fins 107 may be formed such that they have a width at the surface ofthe substrate 101 of between about 5 nm and about 80 nm, such as about30 nm. Additionally, the fins 107 may be spaced apart from each other bya distance of between about 10 nm and about 100 nm, such as about 50 nm.By spacing the fins 107 in such a fashion, the fins 107 may each form aseparate channel region while still being close enough to share a commongate (discussed further below).

Once the first trenches 103 and the fins 107 have been formed, the firsttrenches 103 may be filled with a dielectric material and the dielectricmaterial may be recessed within the first trenches 103 to form the firstisolation regions 105. The dielectric material may be an oxide material,a high-density plasma (HDP) oxide, or the like. The dielectric materialmay be formed, after an optional cleaning and lining of the firsttrenches 103, using either a chemical vapor deposition (CVD) method(e.g., the HARP process), a high density plasma CVD method, or othersuitable method of formation as is known in the art.

The first trenches 103 may be filled by overfilling the first trenches103 and the substrate 101 with the dielectric material and then removingthe excess material outside of the first trenches 103 and the fins 107through a suitable process such as chemical mechanical polishing (CMP),an etch, a combination of these, or the like. In an embodiment, theremoval process removes any dielectric material that is located over thefins 107 as well, so that the removal of the dielectric material willexpose the surface of the fins 107 to further processing steps.

Once the first trenches 103 have been filled with the dielectricmaterial, the dielectric material may then be recessed away from thesurface of the fins 107. The recessing may be performed to expose atleast a portion of the sidewalls of the fins 107 adjacent to the topsurface of the fins 107. The dielectric material may be recessed using awet etch by dipping the top surface of the fins 107 into an etchant suchas HF, although other etchants, such as H₂, and other methods, such as areactive ion etch, a dry etch with etchants such as NH₃/NF₃, chemicaloxide removal, or dry chemical clean may be used. The dielectricmaterial may be recessed to a distance from the surface of the fins 107of between about 50 Å and about 500 Å, such as about 400 Å.Additionally, the recessing may also remove any leftover dielectricmaterial located over the fins 107 to ensure that the fins 107 areexposed for further processing.

As one of ordinary skill in the art will recognize, however, the stepsdescribed above may be only part of the overall process flow used tofill and recess the dielectric material. For example, lining steps,cleaning steps, annealing steps, gap filling steps, combinations ofthese, and the like may also be utilized to form and fill the firsttrenches 103 with the dielectric material. All of the potential processsteps are fully intended to be included within the scope of the presentembodiment.

After the first isolation regions 105 have been formed, a dummy gatedielectric 109, a dummy gate electrode 111 over the dummy gatedielectric 109, and first spacers 113 may be formed over each of thefins 107. In an embodiment the dummy gate dielectric 109 may be formedby thermal oxidation, chemical vapor deposition, sputtering, or anyother methods known and used in the art for forming a gate dielectric.Depending on the technique of gate dielectric formation, the dummy gatedielectric 109 thickness on the top of the fins 107 may be differentfrom the gate dielectric thickness on the sidewall of the fins 107.

The dummy gate dielectric 109 may comprise a material such as silicondioxide or silicon oxynitride with a thickness ranging from about 3angstroms to about 100 angstroms, such as about 10 angstroms. The dummygate dielectric 109 may be formed from a high permittivity (high-k)material (e.g., with a relative permittivity greater than about 5) suchas lanthanum oxide (La₂O₃), aluminum oxide (A1 ₂O₃), hafnium oxide(HfO₂), hafnium oxynitride (HfON), or zirconium oxide (ZrO₂), orcombinations thereof, with an equivalent oxide thickness of about 0.5angstroms to about 100 angstroms, such as about 10 angstroms or less.Additionally, any combination of silicon dioxide, silicon oxynitride,and/or high-k materials may also be used for the dummy gate dielectric109.

The dummy gate electrode 111 may comprise a conductive material and maybe selected from a group comprising of W, Al, Cu, AlCu, W, Ti, TiAlN,TaC, TaCN, TaSiN, Mn, Zr, TiN, Ta, TaN, Co, Ni, combinations of these,or the like. The dummy gate electrode 111 may be deposited by chemicalvapor deposition (CVD), sputter deposition, or other techniques knownand used in the art for depositing conductive materials. The thicknessof the dummy gate electrode 111 may be in the range of about 5 Å toabout 200 Å. The top surface of the dummy gate electrode 111 may have anon-planar top surface, and may be planarized prior to patterning of thedummy gate electrode 111 or gate etch. Ions may or may not be introducedinto the dummy gate electrode 111 at this point. Ions may be introduced,for example, by ion implantation techniques.

Once formed, the dummy gate dielectric 109 and the dummy gate electrode111 may be patterned to form a series of stacks 115 over the fins 107.The stacks 115 define multiple channel regions located on each side ofthe fins 107 beneath the dummy gate dielectric 109. The stacks 115 maybe formed by depositing and patterning a gate mask (not separatelyillustrated in FIG. 1) on the dummy gate electrode 111 using, forexample, deposition and photolithography techniques known in the art.The gate mask may incorporate commonly used masking and sacrificialmaterials, such as (but not limited to) silicon oxide, siliconoxynitride, SiCON, SiC, SiOC, and/or silicon nitride and may bedeposited to a thickness of between about 5 Å and about 200 Å. The dummygate electrode 111 and the dummy gate dielectric 109 may be etched usinga dry etching process to form the patterned stacks 115.

Once the stacks 115 have been patterned, the first spacers 113 may beformed. The first spacers 113 may be formed on opposing sides of thestacks 115. The first spacers 113 are typically formed by blanketdepositing a spacer layer (not separately illustrated in FIG. 1) on thepreviously formed structure. The spacer layer may comprise SiN,oxynitride, SiC, SiON, SiOCN, SiOC, oxide, and the like and may beformed by methods utilized to form such a layer, such as chemical vapordeposition (CVD), plasma enhanced CVD, sputter, and other methods knownin the art. The spacer layer may comprise a different material withdifferent etch characteristics or the same material as the dielectricmaterial within the first isolation regions 105. The first spacers 113may then be patterned, such as by one or more etches to remove thespacer layer from the horizontal surfaces of the structure, to form thefirst spacers 113.

In an embodiment the first spacers 113 may be formed to have a thicknessof between about 5 Å and about 500 Å. Additionally, once the firstspacers 113 have been formed, a first spacer 113 adjacent to one stack115 may be separated from a first spacer 113 adjacent to another stack115 by a distance of between about 5 nm and about 200 nm, such as about20 nm. However, any suitable thicknesses and distances may be utilized.

FIG. 2 illustrates a removal of the fins 107 from those areas notprotected by the stacks 115 and the first spacers 113 and a regrowth ofsource/drain regions 201. The removal of the fins 107 from those areasnot protected by the stacks 115 and the first spacers 113 may beperformed by a reactive ion etch (RIE) using the stacks 115 and thefirst spacers 113 as hardmasks, or by any other suitable removalprocess. The removal may be continued until the fins 107 are eitherplanar with (as illustrated) or below the surface of the first isolationregions 105.

Once these portions of the fins 107 have been removed, a hard mask (notseparately illustrated), is placed and patterned to cover the dummy gateelectrode 111 to prevent growth and the source/drain regions 201 may beregrown in contact with each of the fins 107. In an embodiment thesource/drain regions 201 may be regrown and, in some embodiments thesource/drain regions 201 may be regrown to form a stressor that willimpart a stress to the channel regions of the fins 107 locatedunderneath the stacks 115. In an embodiment wherein the fins 107comprise silicon and the FinFET is a p-type device, the source/drainregions 201 may be regrown through a selective epitaxial process with amaterial, such as silicon or else a material such as silicon germaniumthat has a different lattice constant than the channel regions. Theepitaxial growth process may use precursors such as silane,dichlorosilane, germane, and the like, and may continue for betweenabout 5 minutes and about 120 minutes, such as about 30 minutes.

In an embodiment the source/drain regions 201 may be formed to have athickness of between about 5 Å and about 1000 Å and a first height H₁over the first isolation regions 105 of between about 10 Å and about 500Å, such as about 200 Å. In this embodiment, the source/drain regions 201may be formed to have a height above the upper surface of the firstisolation regions 105 of between about 5 nm and about 250 nm, such asabout 100 nm. However, any suitable height may be utilized.

Once the source/drain regions 201 are formed, dopants may be implantedinto the source/drain regions 201 by implanting appropriate dopants tocomplement the dopants in the fins 107. For example, p-type dopants suchas boron, gallium, indium, or the like may be implanted to form a PMOSdevice. Alternatively, n-type dopants such as phosphorous, arsenic,antimony, or the like may be implanted to form an NMOS device. Thesedopants may be implanted using the stacks 115 and the first spacers 113as masks. It should be noted that one of ordinary skill in the art willrealize that many other processes, steps, or the like may be used toimplant the dopants. For example, one of ordinary skill in the art willrealize that a plurality of implants may be performed using variouscombinations of spacers and liners to form source/drain regions having aspecific shape or characteristic suitable for a particular purpose. Anyof these processes may be used to implant the dopants, and the abovedescription is not meant to limit the present embodiments to the stepspresented above.

Additionally at this point the hard mask that covered the dummy gateelectrode 111 during the formation of the source/drain regions 201 isremoved. In an embodiment the hard mask may be removed using, e.g., awet or dry etching process that is selective to the material of the hardmask. However, any suitable removal process may be utilized.

FIG. 2 also illustrates a formation of an inter-layer dielectric (ILD)layer 203 (illustrated in dashed lines in FIG. 2 in order to moreclearly illustrate the underlying structures) over the stacks 115 andthe source/drain regions 201. The ILD layer 203 may comprise a materialsuch as boron phosphorous silicate glass (BPSG), although any suitabledielectrics may be used. The ILD layer 203 may be formed using a processsuch as PECVD, although other processes, such as LPCVD, mayalternatively be used. The ILD layer 203 may be formed to a thickness ofbetween about 100 Å and about 3,000 Å. Once formed, the ILD layer 203may be planarized with the first spacers 113 using, e.g., aplanarization process such as chemical mechanical polishing process,although any suitable process may be utilized.

FIG. 3 illustrates a cross-sectional view of FIG. 2 along line 3-3′ andalso illustrates a removal and replacement of the material of the dummygate electrode 111 and the dummy gate dielectric 109 with a plurality oflayers for a gate stack 701 (not illustrated in FIG. 3 but illustratedand described below with respect to FIG. 7), including a firstdielectric material 301, a first conductive layer 303, a first metalmaterial 305, a work function layer 307, and a first barrier layer 309.In an embodiment the dummy gate electrode 111 and the dummy gatedielectric 109 may be removed using, e.g., a wet or dry etching processthat utilizes etchants that are selective to the material of the dummygate electrode 111 and the dummy gate dielectric 109. However, anysuitable removal process may be utilized.

The first dielectric material 301 is a high-k material such as HfO₂,HfSiO, HfSiON, HfTaO, HfTiO, HfZrO, LaO, ZrO, Ta₂O₅, combinations ofthese, or the like, deposited through a process such as atomic layerdeposition, chemical vapor deposition, or the like. The first dielectricmaterial 301 may be deposited to a thickness of between about 5 Å andabout 200 Å, although any suitable material and thickness may beutilized.

Optionally, an interfacial layer (not separately illustrated in FIG. 3)may be formed prior to the formation of the first dielectric material301. In an embodiment the interfacial layer may be a material such assilicon dioxide formed through a process such as in situ steamgeneration (ISSG). However, any suitable material or process offormation may be utilized.

The first conductive layer 303 may be a metal silicide material such astitanium silicon nitride (TSN). In an embodiment the first conductivelayer 303 may be formed using a deposition process such as chemicalvapor deposition, although any suitable method of deposition, such as adeposition and subsequent silicidation, may be utilized to a thicknessof between about 5 Å and about 30 Å. However, any suitable thickness maybe utilized.

The first metal material 305 may be formed adjacent to the firstdielectric material 301 as a barrier layer and may be formed from ametallic material such as TaN, Ti, TiAlN, TaC, TaCN, TaSiN, Mn, Zr, TiN,Ru, Mo, WN, other metal oxides, metal nitrides, metal silicates,transition metal-oxides, transition metal-nitrides, transitionmetal-silicates, oxynitrides of metals, metal aluminates, zirconiumsilicate, zirconium aluminate, combinations of these, or the like. Thefirst metal material 305 may be deposited using a deposition processsuch as atomic layer deposition, chemical vapor deposition, sputtering,or the like, to a thickness of between about 5 Å and about 200 Å,although any suitable deposition process or thickness may be used.

The work function layer 307 is formed over the first metal material 305,and the material for the work function layer 307 may be chosen basedupon the type of device desired. Exemplary p-type work function metalsthat may be included include Al, TiAlC, TiN, TaN, Ru, Mo, WN, ZrSi₂,MoSi₂, TaSi₂, NiSi₂, WN, other suitable p-type work function materials,or combinations thereof. Exemplary n-type work function metals that maybe included include Ti, Ag, TaAl, TaAlC, TiAlN, TaC, TaCN, TaSiN, Mn,Zr, other suitable n-type work function materials, or combinationsthereof. A work function value is associated with the materialcomposition of the work function layer 307, and thus, the material ofthe work function layer 307 is chosen to tune its work function value sothat a desired threshold voltage Vt is achieved in the device that is tobe formed in the respective region. The work function layer(s) may bedeposited by CVD, PVD, and/or other suitable process to a thickness ofbetween about 5 Å and about 50 Å.

The first barrier layer 309 may be formed adjacent to the work functionlayer 307 and, in a particular embodiment, may be similar to the firstmetal material 305. For example, the first barrier layer 309 may beformed from a metallic material such as TiN, Ti, TiAlN, TaC, TaCN,TaSiN, Mn, Zr, TaN, Ru, Mo, WN, other metal oxides, metal nitrides,metal silicates, transition metal-oxides, transition metal-nitrides,transition metal-silicates, oxynitrides of metals, metal aluminates,zirconium silicate, zirconium aluminate, combinations of these, or thelike. Additionally, the first barrier layer 309 may be deposited using adeposition process such as atomic layer deposition, chemical vapordeposition, sputtering, or the like, to a thickness of between about 5 Åand about 200 Å, although any suitable deposition process or thicknessmay be used.

FIGS. 4A-4C illustrate a formation of a metal layer 401 over the firstbarrier layer 309, with FIG. 4A illustrating a cross-sectional viewafter formation of the metal layer 401 while FIGS. 4B-4C illustrate adeposition chamber that may be used in an embodiment to form the metallayer 401. In an embodiment the metal layer 401 may be a material thatis both suitable for use as a seed layer to help a subsequent fillingprocess as well as a material that can be used to help block or reducethe transport of fluorine atoms into the work function layer 307. In aparticular embodiment, the metal layer 401 may be crystalline tungsten(W) that is formed free from the presence of fluorine atoms.

FIG. 4B illustrates a deposition system 400 that may be used to form themetal layer 401 using a conformal deposition process such as atomiclayer deposition. In an embodiment the deposition system 400 receivesprecursor materials from a first precursor delivery system 405 and asecond precursor delivery system 406 to form a series of monolayers ofmaterials. In an embodiment the first precursor delivery system 405 andthe second precursor delivery system 406 may work in conjunction withone another to supply the various different precursor materials to adeposition chamber 403 wherein the substrate 101 (and consequently thefirst barrier layer 309) are placed. However, the first precursordelivery system 405 and the second precursor delivery system 406 mayhave physical components that are similar with each other.

For example, the first precursor delivery system 405 and the secondprecursor delivery system 406 may each include a gas supply 407 and aflow controller 409 (labeled in FIG. 4B with regards to the firstprecursor delivery system 405 but not labeled for clarity with respectto the second precursor delivery system 406). In an embodiment in whichthe first precursor is stored in a gaseous state, the gas supply 407 maysupply the first precursor to the deposition chamber 403. The gas supply407 may be a vessel, such as a gas storage tank, that is located eitherlocally to the deposition chamber 403 or else may be located remotelyfrom the deposition chamber 403. Alternatively, the gas supply 407 maybe a facility that independently prepares and delivers the firstprecursor to the flow controller 409. Any suitable source for the firstprecursor may be utilized as the gas supply 407, and all such sourcesare fully intended to be included within the scope of the embodiments.

The gas supply 407 may supply the desired precursor to the flowcontroller 409. The flow controller 409 may be utilized to control theflow of the precursor to the precursor gas controller 413 and,eventually, to the deposition chamber 403, thereby also helping tocontrol the pressure within the deposition chamber 403. The flowcontroller 409 may be, e.g., a proportional valve, a modulating valve, aneedle valve, a pressure regulator, a mass flow controller, combinationsof these, or the like. However, any suitable method for controlling andregulating the flow may be utilized, and all such components and methodsare fully intended to be included within the scope of the embodiments.

However, as one of ordinary skill in the art will recognize, while thefirst precursor delivery system 405 and the second precursor deliverysystem 406 have been described herein as having identical components,this is merely an illustrative example and is not intended to limit theembodiments in any fashion. Any type of suitable precursor deliverysystem, with any type and number of individual components identical toor different from any of the other precursor delivery systems within thedeposition system 400, may alternatively be utilized. All such precursorsystems are fully intended to be included within the scope of theembodiments.

Additionally, in an embodiment in which the first precursor is stored ina solid or liquid state, the gas supply 407 may store a carrier gas andthe carrier gas may be introduced into a precursor canister (notseparately illustrated), which stores the first precursor in the solidor liquid state. The carrier gas is then used to push and carry thefirst precursor as it either evaporates or sublimates into a gaseoussection of the precursor canister before being sent to the precursor gascontroller 413. Any suitable method and combination of units may beutilized to provide the first precursor, and all such combination ofunits are fully intended to be included within the scope of theembodiments.

The first precursor delivery system 405 and the second precursordelivery system 406 may supply their individual precursor materials intothe precursor gas controller 413. The precursor gas controller 413connects and isolates the first precursor delivery system 405 and thesecond precursor delivery system 406 to and from the deposition chamber403 in order to deliver the desired precursor materials to thedeposition chamber 403. The precursor gas controller 413 may includesuch devices as valves, flow meters, sensors, and the like to controlthe delivery rates of each of the precursors, and may be controlled byinstructions received from the control unit 415 (described further belowwith respect to FIG. 4C).

The precursor gas controller 413, upon receiving instructions from thecontrol unit 415, may open and close valves so as to connect one of thefirst precursor delivery system 405 and the second precursor deliverysystem 406 to the deposition chamber 403 and direct a desired precursormaterial through a manifold 426, into the deposition chamber 403, and toa showerhead 417. The showerhead 417 may be utilized to disperse thechosen precursor material into the deposition chamber 403 and may bedesigned to evenly disperse the precursor material in order to minimizeundesired process conditions that may arise from uneven dispersal. In anembodiment the showerhead 417 may have a circular design with openingsdispersed evenly around the showerhead 417 to allow for the dispersal ofthe desired precursor material into the deposition chamber 403.

However, as one of ordinary skill in the art will recognize, theintroduction of precursor materials to the deposition chamber 403through a single showerhead 417 or through a single point ofintroduction as described above is intended to be illustrative only andis not intended to be limiting to the embodiments. Any number ofseparate and independent showerheads 417 or other openings to introduceprecursor materials into the deposition chamber 403 may alternatively beutilized. All such combinations of showerheads and other points ofintroduction are fully intended to be included within the scope of theembodiments.

The deposition chamber 403 may receive the desired precursor materialsand expose the precursor materials to the surface of the first barrierlayer 309, and the deposition chamber 403 may be any desired shape thatmay be suitable for dispersing the precursor materials and contactingthe precursor materials with the sidewalls of the surface of the firstbarrier layer 309. In the embodiment illustrated in FIG. 4B, thedeposition chamber 403 has a cylindrical sidewall and a bottom. However,the deposition chamber 403 is not limited to a cylindrical shape, andany other suitable shape, such as a hollow square tube, an octagonalshape, or the like, may be utilized. Furthermore, the deposition chamber403 may be surrounded by a housing 419 made of material that is inert tothe various process materials. As such, while the housing 419 may be anysuitable material that can withstand the chemistries and pressuresinvolved in the deposition process, in an embodiment the housing 419 maybe steel, stainless steel, nickel, aluminum, alloys of these,combinations of these, and like.

Within the deposition chamber 403 the substrate 101 may be placed on amounting platform 421 in order to position and control the substrate 101during the deposition processes. The mounting platform 421 may includeheating mechanisms in order to heat the substrate 101 during thedeposition processes. Furthermore, while a single mounting platform 421is illustrated in FIG. 4B, any number of mounting platforms 421 mayadditionally be included within the deposition chamber 403.

Additionally, the deposition chamber 403 and the mounting platform 421may be part of a cluster tool system (not shown). The cluster toolsystem may be used in conjunction with an automated handling system inorder to position and place the substrate 101 into the depositionchamber 403 prior to the deposition processes, position, hold thesubstrate 101 during the deposition processes, and remove the substrate101 from the deposition chamber 403 after the deposition processes.

The deposition chamber 403 may also have an exhaust outlet 425 forexhaust gases to exit the deposition chamber 403. A vacuum pump 423 maybe connected to the exhaust outlet 425 of the deposition chamber 403 inorder to help evacuate the exhaust gases. The vacuum pump 423, undercontrol of the control unit 415, may also be utilized to reduce andcontrol the pressure within the deposition chamber 403 to a desiredpressure and may also be utilized to evacuate precursor materials fromthe deposition chamber 403 in preparation for the introduction of thenext precursor material.

FIG. 4C illustrates an embodiment of the control unit 415 that may beutilized to control the precursor gas controller 413 and the vacuum pump423 (as illustrated in FIG. 4B). The control unit 415 may be any form ofcomputer processor that can be used in an industrial setting forcontrolling process machines. In an embodiment the control unit 415 maycomprise a processing unit 402, such as a desktop computer, aworkstation, a laptop computer, or a dedicated unit customized for aparticular application. The control unit 415 may be equipped with adisplay 404 and one or more input/output components 411, such asinstruction outputs, sensor inputs, a mouse, a keyboard, printer,combinations of these, or the like. The processing unit 402 may includea central processing unit (CPU) 408, memory 410, a mass storage device412, a video adapter 424, and an I/O interface 416 connected to a bus418.

The bus 418 may be one or more of any type of several bus architecturesincluding a memory bus or memory controller, a peripheral bus, or videobus. The CPU 408 may comprise any type of electronic data processor, andthe memory 410 may comprise any type of system memory, such as staticrandom access memory (SRAM), dynamic random access memory (DRAM), orread-only memory (ROM). The mass storage device 412 may comprise anytype of storage device configured to store data, programs, and otherinformation and to make the data, programs, and other informationaccessible via the bus 418. The mass storage device 412 may comprise,for example, one or more of a hard disk drive, a magnetic disk drive, oran optical disk drive.

The video adapter 424 and the I/O interface 416 provide interfaces tocouple external input and output devices to the processing unit 402. Asillustrated in FIG. 4C, examples of input and output devices include thedisplay 404 coupled to the video adapter 424 and the I/O component 411,such as a mouse, keyboard, printer, and the like, coupled to the I/Ointerface 416. Other devices may be coupled to the processing unit 402,and additional or fewer interface cards may be utilized. For example, aserial interface card (not shown) may be used to provide a serialinterface for a printer. The processing unit 402 also may include anetwork interface 420 that may be a wired link to a local area network(LAN) or a wide area network (WAN) 422 and/or a wireless link.

It should be noted that the control unit 415 may include othercomponents. For example, the control unit 415 may include powersupplies, cables, a motherboard, removable storage media, cases, and thelike. These other components, although not shown in FIG. 4C, areconsidered part of the control unit 415.

In an embodiment the formation of the metal layer 401 may be initiatedby putting a first precursor material into the first precursor deliverysystem 405. For example, in an embodiment in which the metal layer 401is tungsten (W), the first precursor material may be a precursor that isfree from fluorine atoms, such as tungsten chloride (WCl_(x)), wherein Xmay be 4, 5, 6, and may be placed into the first precursor deliverysystem 405. However, as one of ordinary skill in the art will recognize,this precursor is not the only precursor that may be utilized to form alayer of tungsten, and the use of tungsten chloride is not intended tobe limiting to the embodiments. Any suitable precursor material in anysuitable phase (solid, liquid, or gas) to form a layer of tungsten thatis free from fluorine that may be used to form other materials, may beutilized.

Additionally, a second precursor material may be placed into the secondprecursor delivery system 406. In the embodiment in which a layer oftungsten that is free from fluorine atoms is the desired material forthe metal layer 401, the second precursor material may be a precursormaterial that contains hydrogen in order to react with the firstprecursor material to form a monolayer of tungsten without fluorine. Forexample, in the embodiment in which tungsten chloride (WCl₅) is utilizedas the first precursor material, hydrogen (H₂) may be used as the secondprecursor material and may be placed into the second precursor deliverysystem 406. However, the description of hydrogen as the second precursormaterial is not intended to be limiting to the embodiments, and anyother suitable precursor material, such as SiH₄/NH₃, combinations ofthese, or the like, may be utilized as the second precursor material.

Once the first precursor material and the second precursor material havebeen placed into the first precursor delivery system 405 and the secondprecursor delivery system 406, respectively, the formation of the metallayer 401 may be initiated by the control unit 415 sending aninstruction to the precursor gas controller 413 to connect the firstprecursor delivery system 405 to the deposition chamber 403. Onceconnected, the first precursor delivery system 405 can deliver the firstprecursor material (e.g., the tungsten chloride (WCl₅)) to theshowerhead 417 through the precursor gas controller 413 and the manifold426. The showerhead 417 can then disperse the first precursor materialinto the deposition chamber 403, wherein the first precursor materialcan be adsorbed and react to the exposed surfaces of the first barrierlayer 309.

In the embodiment to form a layer of tungsten free from fluorine atoms,the first precursor material may be flowed into the deposition chamber403 at a flow rate of between about 0.1 standard liter per minute (slm)and about 1 slm for about 0.1-1 seconds per cycle. Additionally, thedeposition chamber 403 may be held at a pressure of between about 5 torrand about 50 torr, such as about 20 torr, and a temperature of betweenabout 400° C. and about 500° C., such as about 450° C. However, as oneof ordinary skill in the art will recognize, these process conditionsare only intended to be illustrative, as any suitable process conditionsmay be utilized while remaining within the scope of the embodiments.

As the first precursor material is adsorbed onto the surfaces of thefirst barrier layer 309, the first precursor material will react withopen active sites located on the exposed surfaces. However, once all ofthe open active sites on the exposed surfaces have reacted with thefirst precursor material, the reaction will stop, as there are no moreopen active sites to which the first precursor material will bond. Thislimitation causes the reaction of the first precursor material with theexposed surfaces of the first barrier layer 309 to be self-limiting andto form a monolayer of the reacted first precursor material on thesurfaces of the first barrier layer 309, thereby allowing for a moreprecise control of the thickness of the metal layer 401.

After the self-limiting reaction has finished, the deposition chamber403 may be purged of the first precursor material. For example, thecontrol unit 415 may instruct the precursor gas controller 413 todisconnect the first precursor delivery system 405 (containing the firstprecursor material to be purged from the deposition chamber 403) and toconnect a purge gas delivery system 414 to deliver a purge gas to thedeposition chamber 403. In an embodiment the purge gas delivery system414 may be a gaseous tank or other facility that provides a purge gassuch as nitrogen, argon, xenon, or other non-reactive gas to thedeposition chamber 403. Additionally, the control unit 415 may alsoinitiate the vacuum pump 423 in order to apply a pressure differentialto the deposition chamber 403 to aid in the removal of the firstprecursor material. The purge gas, along with the vacuum pump 423, maypurge the first precursor material from the deposition chamber 403 forabout 3 seconds.

After the purge of the first precursor material has been completed, theintroduction of the second precursor material (e.g., hydrogen) to thedeposition chamber 403 may be initiated by the control unit 415 sendingan instruction to the precursor gas controller 413 to disconnect thepurge gas delivery system 414 and to connect the second precursordelivery system 406 (containing the second precursor material) to thedeposition chamber 403. Once connected, the second precursor deliverysystem 406 can deliver the second precursor material to the showerhead417. The showerhead 417 can then disperse the second precursor materialinto the deposition chamber 403, wherein the second precursor materialcan be adsorbed on the exposed surfaces of the first barrier layer 309and react with the first precursor material in another self-limitingreaction to form a monolayer of the desired material, e.g., tungstenfree from fluorine, on the exposed surfaces of the first barrier layer309.

In the embodiment discussed above to form a layer of tungsten withtungsten chloride, the hydrogen may be introduced into the depositionchamber 403 at a flow rate of between about 1 slm and about 8 slm, suchas about 6 slm, for about 0.1-1.5 seconds. Additionally, the depositionchamber 403 may be held at a pressure of between about 5 torr and about50 torr and a temperature of between about 400° C. and about 500° C.However, as one of ordinary skill in the art will recognize, theseprocess conditions are only intended to be illustrative, as any suitableprocess conditions may be utilized to introduce oxygen while remainingwithin the scope of the embodiments.

After the monolayer of the desired material, e.g., tungsten, has beenformed, the deposition chamber 403 may be purged (leaving behind themonolayer of the desired material on the exposed surfaces of the firstbarrier layer 309) using, e.g., a purge gas from the purge gas deliverysystem 414 for about three seconds. After the deposition chamber 403 hasbeen purged, a first cycle for the formation of the desired material hasbeen completed, and a set of chemical equations that may describe thechemical processes used in the atomic layer deposition process may beseen below as equations 1 and 2:

WCl_(x)*+H₂→W−H*+HCl

W−H*+WCl₅→W−WCl_(x)*+HCl

Once the first cycle has been finished, a second cycle similar to thefirst cycle may be started. For example, the repeated cycle mayintroduce the first precursor material, purge with the purge gas, pulsewith the second precursor, and purge with the purge gas. These cyclesmay be repeated until the metal layer 401 has a thickness of betweenabout 20 Å and about 50 Å, such as between about 30 Å and about 40 Å.Once the desired thickness of the metal layer 401 has been reached, thesubstrate 101 may be removed from the deposition chamber 403 for furtherprocessing.

However, as one of ordinary skill in the art will recognize, the abovedescribed process to form the metal layer 401 is intended to beillustrative and is not intended to be limiting to the embodiments. Anyother suitable process, such as initially pulsing the second precursormaterial (e.g., hydrogen), purging with the purge gas, introducing thefirst precursor material (e.g., tungsten chloride), and purging with thepurge gas to complete a first cycle and then repeating the first cycle,may be utilized. This and any other suitable process to form the metallayer 401 are fully intended to be included within the scope of theembodiments.

By utilizing a precursor materials such as tungsten chloride that doesnot utilize fluorine atoms, the metal layer 401 may be formed withoutresidual fluorine being incorporated from the deposition process whilestill allowing later depositions to use fluorine based precursor thatare cheaper and quicker. In particular, the tungsten chloride may beformed with a fluorine concentration of about zero. As such, ifsubsequently formed layers do contain residual fluorine atoms from theirindividual deposition processes, the metal layer 401 may act as abarrier layer and prevent the fluorine from diffusing further into thework function layer 307 and interfering with the operation of the metalgate.

FIG. 5 illustrates that, once the metal layer 401 has been formed, anucleation layer 501 may be formed over the metal layer 401 in order toprovide a nucleation point for a subsequent fill material 601 (notillustrated in FIG. 5 but illustrated and discussed below with respectto FIG. 6). In an embodiment the nucleation layer 501 may be the samematerial as the metal layer 401 (e.g., tungsten), may be formed using asimilar process (e.g., ALD), but may be deposited without fluorine freeprecursors. Additionally, while the metal layer 401 may be a crystalline(e.g., crystalline tungsten), the nucleation layer 501 may be formed tobe an amorphous material, such as amorphous tungsten.

The nucleation layer 501 may be formed using a process similar to theformation of the metal layer 401, such as an atomic layer depositionprocess. Additionally, the nucleation layer 501 may be formed eitherwithin the same deposition system 400 as the metal layer 401 (using,e.g., a third precursor delivery system (not separately illustrated), afourth precursor delivery system (not separately illustrated), and afifth precursor delivery system (also not separately illustrated), ormay be a separate deposition system using similar, but not necessarilythe same, equipment as described. As such, for the convenience of thisdiscussion, the following discussion is described in terms of thedeposition system 400 above, it should be understood that the discussionis not limited to the same deposition system as was used to deposit themetal layer 401.

In a particular embodiment the formation of the nucleation layer 501 maybe initiated by putting a first nucleation precursor material into thefirst precursor delivery system 405. For example, in an embodiment inwhich the metal layer 401 is tungsten (W), the first nucleationprecursor material may be a precursor such as silane (SiH₄) and may beplaced into the first precursor delivery system 405. However, as one ofordinary skill in the art will recognize, this precursor is not the onlyprecursor that may be utilized to form a layer of tungsten, and the useof silane is not intended to be limiting to the embodiments. Forexample, the first nucleation precursor material may be a material suchas diborane (B₂H₆). Any suitable precursor material in any suitablephase (solid, liquid, or gas) to form a layer of tungsten may be used.

Additionally, a second nucleation precursor material may be placed intothe second precursor delivery system 406. In the embodiment in which alayer of tungsten is the desired material for the nucleation layer, thesecond nucleation precursor material may be a precursor material thatcontains tungsten in order to react with the first precursor material toform a monolayer of tungsten. For example, in the embodiment in whichsilane (SiH₄) is utilized as the first nucleation precursor material,tungsten fluoride (WF₆) may be used as the second nucleation precursormaterial and may be placed into the second precursor delivery system406. However, any other suitable precursor material or combinations ofmaterials may be utilized as the second nucleation precursor material.

Once the first nucleation precursor material and the second nucleationprecursor material have been placed into the first precursor deliverysystem 405 and the second precursor delivery system 406, respectively,the formation of the nucleation layer 501 may be initiated by thecontrol unit 415 sending an instruction to the precursor gas controller413 to connect the first precursor delivery system 405 to the depositionchamber 403. Once connected, the first precursor delivery system 405 candeliver the first nucleation precursor material (e.g., the silane) tothe showerhead 417 through the precursor gas controller 413 and themanifold 426. The showerhead 417 can then disperse the first nucleationprecursor material into the deposition chamber 403, wherein the firstnucleation precursor material can be adsorbed and react to the exposedsurfaces of the metal layer 401.

In the embodiment to form a layer of tungsten as the nucleation layer501, the first nucleation precursor material may be flowed into thedeposition chamber 403 at a flow rate of between about 0.1 slm and about1 slm for about 1˜3 seconds per cycle. Additionally, the depositionchamber 403 may be held at a pressure of between about 2 torr and about10 torr, such as about 5 torr, and a temperature of between about 200°C. and about 400° C., such as about 300° C. However, as one of ordinaryskill in the art will recognize, these process conditions are onlyintended to be illustrative, as any suitable process conditions may beutilized while remaining within the scope of the embodiments.

As the first nucleation precursor material is adsorbed onto the surfacesof the metal layer 401, the first nucleation precursor material willreact with open active sites located on the exposed surfaces. However,once all of the open active sites on the exposed surfaces have reactedwith the first nucleation precursor material, the reaction will stop, asthere are no more open active sites to which the first nucleationprecursor material will bond. This limitation causes the reaction of thefirst nucleation precursor material with the exposed surfaces of themetal layer 401 to be self-limiting and to form a monolayer of thereacted first nucleation precursor material on the surfaces of the metallayer 401, thereby allowing for a more precise control of the thicknessof the nucleation layer 501.

After the self-limiting reaction has finished, the deposition chamber403 may be purged of the first nucleation precursor material. Forexample, the control unit 415 may instruct the precursor gas controller413 to disconnect the first precursor delivery system 405 (containingthe first nucleation precursor material to be purged from the depositionchamber 403) and to connect the purge gas delivery system 414 to deliverthe purge gas to the deposition chamber 403. Additionally, the controlunit 415 may also initiate the vacuum pump 423 in order to apply apressure differential to the deposition chamber 403 to aid in theremoval of the first precursor material. The purge gas, along with thevacuum pump 423, may purge the first nucleation precursor material fromthe deposition chamber 403 for about 3 seconds.

After the purge of the first nucleation precursor material has beencompleted, the introduction of the second nucleation precursor material(e.g., tungsten fluoride) to the deposition chamber 403 may be initiatedby the control unit 415 sending an instruction to the precursor gascontroller 413 to disconnect the purge gas delivery system 414 and toconnect the second precursor delivery system 406 (containing the secondnucleation precursor material) to the deposition chamber 403. Onceconnected, the second precursor delivery system 406 can deliver thesecond nucleation precursor material to the showerhead 417. Theshowerhead 417 can then disperse the second nucleation precursormaterial into the deposition chamber 403, wherein the second nucleationprecursor material can be adsorbed on the exposed surfaces of the metallayer 401 and react with the first nucleation precursor material inanother self-limiting reaction to form a monolayer of the desiredmaterial, e.g., tungsten, on the exposed surfaces of the metal layer401.

In the embodiment discussed above to form a layer of tungsten, thetungsten fluoride may be introduced into the deposition chamber 403 at aflow rate of between about 0.01 slm and about 0.2 slm, such as about 0.1slm, for about 1˜3 seconds. Additionally, the deposition chamber 403 maybe held at a pressure of between about 2 torr and about 10 torr and atemperature of between about 200° C. and about 400° C. However, as oneof ordinary skill in the art will recognize, these process conditionsare only intended to be illustrative, as any suitable process conditionsmay be utilized to introduce the tungsten fluoride while remainingwithin the scope of the embodiments.

After the monolayer of the desired material, e.g., tungsten, has beenformed, the deposition chamber 403 may be purged (leaving behind themonolayer of the desired material on the exposed surfaces of the metallayer 401) using, e.g., the purge gas from the purge gas delivery system414 for about three seconds. After the deposition chamber 403 has beenpurged, a first cycle for the formation of the desired material has beencompleted, and a second cycle similar to the first cycle may be started.For example, the repeated cycle may introduce the first nucleationprecursor material, purge with the purge gas, pulse with the secondnucleation precursor material, and purge with the purge gas. Thesecycles may be repeated until the nucleation layer 501 has a thickness ofbetween about 20 Å and about 40 Å. Once the desired thickness of thenucleation layer 501 has been reached, the substrate 101 may be removedfrom the deposition chamber 403 for further processing.

However, as one of ordinary skill in the art will recognize, the abovedescribed process to form the nucleation layer 501 is intended to beillustrative and is not intended to be limiting to the embodiments. Anyother suitable process, such as initially pulsing the second nucleationprecursor material (e.g., tungsten fluoride), purging with the purgegas, introducing the first nucleation precursor material (e.g., silaneor diborane), and purging with the purge gas to complete a first cycleand then repeating the first cycle, may be utilized. This and any othersuitable process to form the nucleation layer 501 are fully intended tobe included within the scope of the embodiments.

FIG. 6 illustrates that, once the nucleation layer 501 has been formed,a fill material 601 is deposited to fill a remainder of the openingusing the nucleation layer 501 to help nucleate the fill material 601.In an embodiment the fill material 601 may be the same material as thenucleation layer 501 (e.g., tungsten) or may be a different material,such as Al, Cu, AlCu, W, Ti, TiAlN, TaC, TaCN, TaSiN, Mn, Zr, TiN, Ta,TaN, Co, Ni, combinations of these, or the like, to a thickness ofbetween about 1000 Å and about 2000 Å, such as about 1500 Å. However,any suitable material may be utilized.

Additionally, the fill material 601 may be deposited using a depositionprocess such as a non-conformal deposition process such as chemicalvapor deposition. In an embodiment the deposition process may utilizeprecursors such as tungsten fluoride (WF₆) and hydrogen (H₂), althoughany suitable precursors may be utilized. In a particular embodimentusing tungsten fluoride and hydrogen as the precursors, the tungstenfluoride may be flowed into a reaction chamber at a flow rate of betweenabout 0.1 slm and about 0.5 slm, such as about 0.3 slm, while thehydrogen may be flowed in at the same time at a flow rate of betweenabout 1 slm and about 10 slm, such as about 6 slm. Additionally, thechemical vapor deposition process may be performed at a temperature ofbetween about 200° C. and about 400° C., such as about 300° C., and at apressure of between about 100 torr and about 400 torr, such as about 250torr. However, any suitable process conditions may be utilized.

FIG. 7 illustrates that, after the fill material 601 has been depositedto fill and overfill the opening, the materials of the first dielectricmaterial 301, first conductive layer 303, first metal material 305, workfunction layer 307, first barrier layer 309, metal layer 401, nucleationlayer 501, fill material 601 may be planarized to form the gate stack701. In an embodiment the materials may be planarized with the firstspacers 113 using, e.g., a chemical mechanical polishing process,although any suitable process, such as grinding or etching, may beutilized.

After the materials of the gate stack 701 have been formed andplanarized, the materials of the gate stack 701 may be recessed andcapped with a capping layer 703. In an embodiment the materials of thegate stack 701 may be recessed using, e.g., a wet or dry etching processthat utilizes etchants selective to the materials of the gate stack 701.In an embodiment the materials of the gate stack 701 may be recessed adistance of between about 5 nm and about 150 nm, such as about 120 nm.However, any suitable process and distance may be utilized.

Once the materials of the gate stack 701 have been recessed, the cappinglayer 703 may be deposited and planarized with the first spacers 113. Inan embodiment the capping layer 703 is a material such as SiN, SiON,SiCON, SiC, SiOC, combinations of these, or the like, deposited using adeposition process such as atomic layer deposition, chemical vapordeposition, sputtering, or the like. The capping layer 703 may bedeposited to a thickness of between about 5 Å and about 200 Å, and thenplanarized using a planarization process such as chemical mechanicalpolishing such that the capping layer 703 is planar with the firstspacers 113.

FIG. 8 illustrates a formation of a first opening 801 through the ILDlayer 203 in order to expose the source/drain regions 201 in preparationfor formation of a first contact 803. In an embodiment the first opening801 may be formed by initially placing and patterning a firstphotoresist (not separately illustrated) over the source/drain regions201 and then using the first photoresist as a mask with an etchingprocess to form the first opening 801. However, any suitable type ofphotosensitive material or combination of materials may be utilized.

Optionally, a silicide contact (not illustrated) may be formed and thenthe first opening 801 may be filled to form the first contact 803. Thesilicide contact may comprise titanium, nickel, cobalt, or erbium inorder to reduce the Schottky barrier height of the contact. However,other metals, such as platinum, palladium, and the like, may also beused. The silicidation may be performed by blanket deposition of anappropriate metal layer, followed by an annealing step which causes themetal to react with the underlying exposed silicon. Un-reacted metal isthen removed, such as with a selective etch process. The thickness ofthe silicide contact may be between about 5 nm and about 50 nm.

In an embodiment the first contact 803 may be a conductive material suchas W, Al, Cu, AlCu, W, TaC, TaCN, TaSiN, Mn, Zr, TiN, Ta, TaN, Co, Ni,Ti, TiAlN, Ru, Mo, or WN, although any suitable material, such asaluminum, copper, alloys of these, combinations of these, or the like,and may be deposited into the first opening 801 using a depositionprocess such as sputtering, chemical vapor deposition, electroplating,electroless plating, or the like, to fill and/or overfill the firstopening 801. Once filled or overfilled, any deposited material outsideof the first opening 801 may be removed using a planarization processsuch as chemical mechanical polishing (CMP), and the first contact 803may have a thickness of between about 5 Å and about 2000 Å. However, anysuitable material and process of formation may be utilized.

FIG. 9 illustrates a formation of a first etch stop layer 901 over thegate stacks 205. In one embodiment, the first etch stop layer 901 may beformed of silicon nitride using plasma enhanced chemical vapordeposition (PECVD), although other materials such as SiON, SiCON, SiC,SiOC, SiC_(x)N_(y), SiO_(x), other dielectrics, combinations thereof, orthe like, and alternative techniques of forming the first etch stoplayer 901, such as low pressure CVD (LPCVD), PVD, or the like, couldalternatively be used. The first etch stop layer 901 may have athickness of between about 5 Å and about 500 Å.

FIG. 9 also illustrates a formation of a first dielectric layer 903 overthe first etch stop layer 901. The first dielectric layer 903 may bemade of one or more suitable dielectric materials such as low-kdielectrics such as carbon doped oxides, extremely low-k dielectricssuch as porous carbon doped silicon dioxide, silicon oxide, siliconnitride, a polymer such as polyimide, combinations of these, or thelike. The first dielectric layer 903 may be formed through a processsuch as a spin-on process or a chemical vapor deposition (CVD), althoughany suitable process may be utilized, and may have a thickness ofbetween about 5 Å and about 500 Å, such as about 50 Å.

FIG. 9 also illustrates a patterning of both the first dielectric layer903 and the first etch stop layer 901 to form second openings 905 thatexpose the first contact 803 and the gate stack 701. In an embodimentthe first dielectric layer 903 and the first etch stop layer 901 may bepatterned by initially placing and patterning a second photoresist overthe first dielectric layer 903 and then using the second photoresist asa mask during one or more etching processes in order to expose the firstcontact 803 and the gate stack 701. Additionally, after the first etchstop layer 901 has been opened, the etching may either be stoppedwithout extending into the first contact 803 or else may be continued toslightly overetch and form the second opening 905 to extend partiallyinto the first contact 803.

Once the first contact 803 and the gate stack 701 have been exposed, aconductive material may be deposited to fill and/or overfill the secondopenings 905 to make electrical connection with the first contact 803and the gate stack 701. In an embodiment the second contact 907 may be aconductive material such as tungsten (W), although any suitablematerial, such as aluminum, copper, alloys of these, combinations ofthese, or the like, and may be deposited using a deposition process suchas sputtering, chemical vapor deposition, electroplating (with a seedlayer), electroless plating, or the like, to fill and/or overfill thesecond openings 905. Once filled or overfilled, any deposited materialoutside of the second openings 905 may be removed using a planarizationprocess such as chemical mechanical polishing (CMP).

However, while a single process to form the second contacts 907 has beendescribed, one of ordinary skill in the art will understand that othersuitable processes may also be utilized. For example, a first process toform openings and one of the second contacts 907 to make electricalconnection to the first contact 803 may be performed separately from asecond process to form the openings and one of the second contacts 907to the gate stack 701. Any suitable number of processes may be utilizedto form the second contacts 907.

Once the second contacts 907 have been formed, the semiconductor device100 is ready for additional processing. In some embodiments theadditional processing may include forming one or more metallizationlayers over the second contact 907 in order to form functionalcircuitry, forming contact pads in electrically connection with themetallization layer, and packaging the semiconductor device 100 so thatthe semiconductor device 100 may be attached to other external devices.

By forming the metal layer 401 to be free from fluorine, the metal layer401 may act as a barrier layer to block the movement of any residualfluorine that may be present within the nucleation layer 501 or the fillmaterial 601. As such, this residual fluorine is prevented from beingintroduced to the work function layer 307, thereby reducing orpreventing poisoning and degradation of performance from this fluorineand maintaining a lower resistivity. Additionally, without the fluorineentering the work function layer 307, additional atoms from the materialof the work function layer 307 (e.g., aluminum) may diffuse towards theinterface between the first conductive layer 303 and the gate dielectricmaterial 301 (e.g., HfO₂). As such, a more efficient and controlleddevice may be obtained.

FIGS. 10A-10B illustrate charts of relative atomic percentages ofchlorine by-product (in FIG. 10A) and fluorine by-product (in FIG. 10B)that have diffused into the work function layer 307 for embodiments inwhich the metal layer 401 is not present (labeled 1001), an embodimentin which the metal layer 401 has a thickness of 30 Å (labeled 1003), andan embodiment in which the metal layer 401 has a thickness of 50 Å(labeled 1005). These charts were generated using an XPS analysisperformed with 200 μm monochromatic Al K-alpha X-ray, PE 100 eV and 0.2eV step extracted with a 1 kV argon ion sputter. As can be seen in thesefigures, in embodiments in which the metal layer 401 is not present,there is an increased percentage of fluorine (and, accordingly, offluorine poisoning) while there is a decreased percentage of chlorine.Similarly, both embodiments in which the metal layer 401 is present,there is a decreased percentage of fluorine (e.g., between about0.1%-atomic to about 1.5%-atomic, such as about equal to or less thanabout 0.5%-atomic) and an increased percentage of chlorine.

In accordance with an embodiment, a method includes depositing a workfunction layer over a substrate; depositing a barrier layer over thework function layer; depositing a fluorine-free metal layer over thebarrier layer; depositing a first metal layer over the fluorine-freemetal layer; and depositing a second metal layer over the first metallayer to form a gate stack. In an embodiment the depositing the secondmetal layer comprises a fluorine-metal precursor. In an embodiment thefluorine-free metal layer comprises tungsten (W). In an embodiment thefirst metal layer and the second metal layer comprise W. In anembodiment the depositing the fluorine-free metal layer utilizes afluorine-free precursor that also comprises tungsten. In an embodimentthe fluorine-free precursor is tungsten chloride.

In accordance with another embodiment, a method includes depositing awork function layer over a substrate, the work function layer comprisingaluminum; depositing a barrier layer over the work function layer, thebarrier layer comprising titanium nitride; using a first fluorine-freeatomic layer deposition process, depositing a first metal layer over thebarrier layer; depositing a second metal layer over the first metallayer, wherein the depositing the second metal layer is performed atleast in part with a second atomic layer deposition process; and using afluorine-metal precursor, depositing a third metal layer over the secondmetal layer, wherein the depositing the third metal layer is performedat least in part with a chemical vapor deposition process. In anembodiment the first metal layer, the second metal layer, and the thirdmetal layer comprise tungsten (W). In an embodiment the fluorine-metalprecursor comprises W and fluorine. In an embodiment the firstfluorine-free atomic layer deposition process uses tungsten chloride. Inan embodiment the second atomic layer deposition process utilizessilane. In an embodiment the second atomic layer deposition processutilizes diborane. In an embodiment the first fluorine-free atomic layerdeposition process forms the first metal layer as a crystalline materialand wherein the depositing the second metal layer forms the second metallayer as an amorphous material. In an embodiment the method furtherincludes planarizing the third metal layer with first spacers.

In yet another embodiment a device includes a high-K dielectric layerover a substrate; a first barrier layer over the high-K dielectriclayer; a work function layer over the high-K dielectric layer, whereinthe work function layer has a fluorine concentration of between about0.1%-atomic and about 1.5%-atomic; a second barrier layer over the workfunction layer; a conductive layer over the second barrier layer; afirst metal layer over the conductive layer, the first metal layercomprising a fluorine by-product; and a second metal layer over thefirst metal layer, the second metal layer comprising a fluorineby-product. In an embodiment the conductive layer comprises a pluralityof monolayers. In an embodiment the first metal layer comprises aplurality of monolayers. In an embodiment the conductive layer, thefirst metal layer, and the second metal layer comprise tungsten. In anembodiment the conductive layer is crystalline. In an embodiment thefirst metal layer is amorphous

The foregoing outlines features of several embodiments so that thoseskilled in the art may better understand the aspects of the presentdisclosure. Those skilled in the art should appreciate that they mayreadily use the present disclosure as a basis for designing or modifyingother processes and structures for carrying out the same purposes and/orachieving the same advantages of the embodiments introduced herein.Those skilled in the art should also realize that such equivalentconstructions do not depart from the spirit and scope of the presentdisclosure, and that they may make various changes, substitutions, andalterations herein without departing from the spirit and scope of thepresent disclosure.

What is claimed is:
 1. A method of manufacturing a semiconductor device,the method comprising: depositing a work function layer over asemiconductor fin; depositing a barrier layer over the work functionlayer; introducing a first precursor to the work function layer, thefirst precursor being free from fluorine; introducing a second precursorto the work function layer, the second precursor being free fromfluorine, wherein the first precursor and the second precursor form alayer of tungsten; introducing a third precursor to the layer oftungsten, the third precursor comprising silane; introducing a fourthprecursor to the layer of tungsten, the fourth precursor comprisingfluorine, wherein the third precursor and the fourth precursor forms asecond layer of tungsten; and simultaneously introducing the fourthprecursor and a fifth precursor to the second layer of tungsten todeposit a fill material.
 2. The method of claim 1, wherein the firstprecursor is tungsten chloride and the second precursor is hydrogen. 3.The method of claim 1, wherein the first precursor is tungsten chlorideand the second precursor comprises silane.
 4. The method of claim 1,wherein the layer of tungsten has a thickness of between about 20 Å andabout 50 Å.
 5. The method of claim 1, wherein after the introducing thesecond precursor the layer of tungsten has a fluorine concentration ofabout zero.
 6. The method of claim 1, wherein the layer of tungsten iscrystalline.
 7. The method of claim 6, wherein the second layer oftungsten is amorphous.
 8. A method of manufacturing a semiconductordevice, the method comprising: depositing a first layer of tungstenusing a fluorine-free atomic layer deposition process; depositing asecond layer of tungsten using a fluorine-included atomic layerdeposition process; and depositing a fill material of tungsten using achemical vapor deposition process.
 9. The method of claim 8, wherein thefluorine-free atomic layer deposition process utilizes tungsten chlorideand hydrogen.
 10. The method of claim 9, wherein the fluorine-includedatomic layer deposition process utilizes tungsten fluoride and silane.11. The method of claim 10, wherein the chemical vapor depositionprocess utilizes tungsten fluoride and hydrogen.
 12. The method of claim8, wherein the chemical vapor deposition process is a non-conformaldeposition process.
 13. The method of claim 8, wherein the first layerof tungsten has a thickness of between about 20 Å and about 50 Å. 14.The method of claim 13, wherein the second layer of tungsten has athickness of between about 20 Å and about 40 Å.
 15. A method ofmanufacturing a semiconductor device, the method comprising: depositinga work function layer over a channel region of a semiconductor material;depositing a barrier layer over the work function layer; using a firstatomic layer deposition process to sequentially introduce a series offluorine-free precursors to form a crystalline material; using a secondatomic layer deposition process to sequentially introduce a series ofprecursors to form an amorphous material, at least one of the series ofprecursors comprising fluorine; and using a first chemical vapordeposition process to simultaneously introduce a plurality of precursorsto form a fill material.
 16. The method of claim 15, wherein thecrystalline material is tungsten.
 17. The method of claim 16, whereinthe amorphous material is tungsten.
 18. The method of claim 17, whereinthe fill material is tungsten.
 19. The method of claim 15, wherein thesecond atomic layer deposition process utilizes silane.
 20. The methodof claim 15, wherein the first atomic layer deposition process utilizestungsten chloride.